CN103757640A - Micro emulsion type water-based metal anti-rusting liquid - Google Patents
Micro emulsion type water-based metal anti-rusting liquid Download PDFInfo
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- CN103757640A CN103757640A CN201410000991.3A CN201410000991A CN103757640A CN 103757640 A CN103757640 A CN 103757640A CN 201410000991 A CN201410000991 A CN 201410000991A CN 103757640 A CN103757640 A CN 103757640A
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Abstract
The invention discloses a micro emulsion type water-based metal anti-rusting liquid which is prepared from the following raw materials in percentage by mass: 0-10% of anti-rusting agent, 3-20% of base oil, 0-10% of surfactant, 5-20% of corrosion inhibitor, 0.5-1.5% of stabilizing agent, 0-1% of thickening agent, 0-5% of pH adjusting agent and the balance of deionized water. By adopting the anti-rusting liquid, both the defect that an existing anti-rusting liquid such as an oil-based anti-rusting liquid is large in elimination difficulty and not easy to decompose and the defect that the anti-rusting effect of an existing water-based anti-rusting liquid cannot meet the anti-rusting effect of an oil-based anti-rusting liquid are solved, and the advantages of two anti-rusting liquids are integrated, so that the anti-rusting liquid disclosed by the invention has good functions of lubrication, cooling, anti-rusting and the like, and meanwhile the requirements of environmental-friendliness, economy and high efficiency are met.
Description
Technical field
The present invention relates to a kind of metal rust-inhibiting liquid, particularly a kind of micro-emulsion type water-based metal antirust liquid.
Background technology
The corrosion of metal is the problem often running in producing, metal rusting not only makes metal works itself be damaged at aspects such as profile, color and luster and mechanical propertys, and make the Quality Down of product, especially severe also can make product rejection, within 2011, China GDP is 7.43 trillion dollars, and the financial loss causing because of corrosion is up to 2200～3,700 hundred million dollars, accounts for 3%～5% of national GDP total value.In order to slow down the corrosion of iron and steel, the loss that corrosion is caused drops to bottom line, and people have taked a lot of rust protection measures, and wherein the use of rust protection liquid is to apply wide, significantly one of effect.
Rust protection liquid is a kind of synthetic permeate agent of super grade high efficiency, and it can form thin film in metallic surface, prevents corrosion of metal.According to the difference of component, rust protection liquid is divided into oil base rust protection liquid and aqueous protective fluids.
Oil base rust protection liquid is comprised of base oil, oil-soluble inhibitor and supplementary additive etc.Oil base rust protection liquid can form in metallic surface the fine and close oil film of one deck, and water in air-isolation, oxygen etc. play rust inhibition.But oil base rust protection liquid subsequent handling need be carried out oil removing, the removal difficulty of slushing oil is quite large, and along with the continuous enhancing of petroleum resources growing tension and environmental consciousness, adds the existence that oil is difficult for the problems such as decomposition, and oil base rust protection liquid is replaced gradually.
Aqueous protective fluids is comprised of water soluble anti-rust agent, water-soluble additive, inhibiter and water etc.Aqueous protective fluids is in the aqueous solution, to add a certain amount of rust-preventive agent, to stop the generation of chemistry or electrochemical action, generates insoluble passivation film or reacts rete and play rust inhibition.But this class rust protection liquid is applied to behind metallic surface, and liquid film easily trickles, after moisture evaporation, also can in metallic surface, form one deck bloom, lose due rust-proof effect, rustless property does not reach the effect of slushing oil.And traditional aqueous protective fluids contains the compositions such as nitrite, dichromate more, well-known, nitrites is carcinogenic substance, and operator's health is had to harm, and dichromate composition is because containing the heavy metals such as chromium simultaneously, environment is harmful to, has also affected performance and the quality of metal.Therefore, development of new environment-friendly type metal rust protection liquid has been the task of top priority.
Summary of the invention
The object of the present invention is to provide a kind of micro-emulsion type water-based metal antirust liquid, composite collaborative antirust with components such as borate, trolamines, add appropriate base oil to do lubricant simultaneously.Eliminate the shortcoming of oil base and aqueous protective fluids, the advantage of two kinds of rust protection liquids has been rolled into one simultaneously, there is the good function such as lubricated, cooling, antirust.
The technical scheme of micro-emulsion type water-based metal antirust liquid of the present invention is as follows:
A kind of micro-emulsion type water-based metal antirust liquid, its mass percent is as follows:
Wherein:
(1) rust-preventive agent
Rust-preventive agent is organic corrosion inhibitor, i.e. fatty acid soaps, sulfonate, one or more in alcamines, acid amides, ester class.Preferably two or more rust-preventive agent is composite collaborative antirust.
(2) base oil
Base oil is one or more in machinery oil, vegetables oil, white oil, silicone oil, kerosene.
(3) tensio-active agent
Tensio-active agent is one or more in Sodium dodecylbenzene sulfonate (anion surfactant LAS), polyoxyethylenated alcohol sodium sulfate (anion surfactant AES), sorbitan fatty acid ester Soxylat A 25-7 (non-ionic surfactant Tween series), sorbitan fatty acid ester (nonionogenic tenside sapn series), fatty alcohol-polyoxyethylene ether (nonionogenic tenside AEO series).
Tensio-active agent is preferably anion surfactant and nonionogenic tenside is composite.
(4) other auxiliary agent
The auxiliary adding in the present invention also has inhibiter, stablizer, thickening material, PH conditioning agent.
In rust protection liquid, conventionally use inhibiter and rust-preventive agent synergy, inhibiter is often selected alcamines and sour composite use.Alcamines can be selected one or more in monoethanolamine, diethanolamine, trolamine.Acid can be selected one or more in oleic acid, coconut oil, boric acid.
Stablizer can be selected one or more in ethanol, Virahol, propyl carbinol, n-hexyl alcohol.
Thickening material can be selected one or more in sodium cellulose glycolate, sodium hydroxyethyl cellulose, polyoxyethylene glycol.
PH conditioning agent can be selected mineral alkali or ammoniacal liquor, and mineral alkali can be selected sodium carbonate.
Beneficial effect:
The kind of existing water soluble anti-rust agent is a lot, mainly contains inorganic inhibitor and organic corrosion inhibitor two classes.Conventional inorganic inhibitor has Sodium Nitrite, potassium bichromate, molybdate, tungstate etc.But because these rust-preventive agent are conventionally poisonous and environment is had to pollution, therefore its use is restricted, and the present invention adopts organic corrosion inhibitor, environmental protection, environmentally safe.
Although traditional water-based metal antirust liquid has good cooling, security, film-formation result is poor, and the bright aqueous protective fluids of this law has added appropriate base oil to make membrane-forming agent.Base oil is not only the carrier of emulsifying agent and rust-preventive agent; and the protective membrane that can form in metallic surface even compact, makes the adsorption film of rust-preventive agent molecule tightr, also make the not firm rust-preventive agent molecule of absorption be difficult for desorption; thereby strengthened water molecules, what the corrosive mediums such as oxygen were invaded stops.
Surfactant molecule is dimerous by polar group and non-polar group, the former hydrophilic water soluble, the latter's oleophylic oil-soluble.Rust protection liquid of the present invention is owing to having added tensio-active agent; under the effect of strong stirring; when disperse phase is dispersed into many small dropletss; last layer tensio-active agent can be adsorbed in drop surface; its lipophilic group stretches to oil phase; hydrophilic radical stretches to water; and form one deck unit molecule interfacial film; this stratum boundary facial mask has some strength; therefore drop is had to provide protection; when drop is collided mutually, be unlikely mutually and flock together, can make immiscible profit two-phase generation emulsification form stable emulsion.
Tensio-active agent of the present invention adopts emulsifying property good, and has certain cleaning and the aniorfic surfactant of lubricity, preferably with the composite use of nonionic surface active agent, its better effects if.
The invention provides a kind of micro-emulsion type water-based metal antirust liquid, not only both solved existing rust protection liquid as large in oil base rust protection liquid removal difficulty, not labile shortcoming, solve again the shortcoming that existing aqueous protective fluids rust-proof effect does not reach oil base rust protection liquid rust-proof effect, met the requirement of environmental protection, economical and efficient simultaneously.
Micro-emulsion type water-based metal antirust liquid of the present invention, can configure different concentration according to concrete operating mode, is generally 20～30 times of uses of dilution, has advantages of environmental protection, efficient, economic.Be mainly used in the metal rust preventing in machinery production, processing and transportation.
Embodiment
Below in conjunction with embodiment, the specific embodiment of the present invention is described in further detail.Following examples are used for illustrating the present invention, but are not used for limiting the scope of the invention.
Embodiment 1:
(1) in four-hole boiling flask, add 12g silicone oil, then add successively 3g polysorbas20 and 2g sorbester p17, heated and stirred, rotating speed is controlled at 900r/min, and temperature is controlled at 70 ℃.
(2) 5g sodium carbonate, 15g monoethanolamine borate, 10g trolamine, 2g polyoxyethylene glycol are dissolved in appropriate deionized water successively, treat to dissolve completely, be slowly added drop-wise in (1).
(3) mixed solution in (2) is continued to constant temperature and stir 1h.
(4) stir the backward above-mentioned solution of end and add 2g sodium cellulose glycolate, 2g propyl carbinol, supply surplus deionized water to 250g, the rotating speed that slows down, to 200r/min, continues stirring at normal temperature 30min..
The formula composition of table one embodiment 1
| Component title | Content, %(m/m) |
| Trolamine | 4 |
| Silicone oil | 4.8 |
| Polysorbas20 (nonionogenic tenside) | 1.2 |
| Sorbester p17 (nonionogenic tenside) | 0.8 |
| Monoethanolamine borate | 6 |
| Sodium carbonate | 2 |
| Polyoxyethylene glycol | 0.8 |
| Sodium cellulose glycolate | 0.8 |
| Propyl carbinol | 0.8 |
| Deionized water | 78.8 |
Embodiment 2:
(1) in four-hole boiling flask, add 12g kerosene, then add successively 4.5g tween 80 and 0.5g sorbester p17, heated and stirred, rotating speed is controlled at 900r/min, and temperature is controlled at 50 ℃.
(2) 15g monoethanolamine borate, 15g trolamine, 2g polyoxyethylene glycol are dissolved in appropriate deionized water successively, treat to dissolve completely, be slowly added drop-wise in (1).
(3) mixed solution in (2) is continued to constant temperature and stir 1h.
(4) stir the backward above-mentioned solution of end and add 2g sodium cellulose glycolate, 2g propyl carbinol, 10g ammoniacal liquor, supply surplus deionized water to 250g, the rotating speed that slows down, to 200r/min, continues stirring at normal temperature 30min..
The formula composition of table two embodiment 2
| Component title | Content, %(m/m) |
| Trolamine | 6 |
| Kerosene | 4.8 |
| Tween 80 (nonionogenic tenside) | 1.8 |
| Sorbester p17 (nonionogenic tenside) | 0.2 |
| Monoethanolamine borate | 6 |
| Ammoniacal liquor | 4 |
| Polyoxyethylene glycol | 0.8 |
| Sodium cellulose glycolate | 0.8 |
| Propyl carbinol | 0.8 |
| Deionized water | 74.8 |
Embodiment 3:
(1) in four-hole boiling flask, add 10g machinery oil, then add successively 0.75g AEO-3,0.5g AEO-7,1.25g AEO-9, heated and stirred, rotating speed is controlled at 500r/min, and temperature is controlled at 50 ℃.
(2) 5g sodium carbonate, 20g monoethanolamine borate, 20g trolamine, 2g polyoxyethylene glycol are dissolved in appropriate deionized water successively, treat to dissolve completely, be slowly added drop-wise in (1).
(3) mixed solution in (2) is continued to constant temperature and stir 1h.
(4) stir the backward above-mentioned solution of end and add 2g sodium cellulose glycolate, 5g propyl carbinol, supply surplus deionized water to 250g, the rotating speed that slows down, to 200r/min, continues stirring at normal temperature 30min..
The formula composition of table three embodiment 3
| Component title | Content, %(m/m) |
| Trolamine | 8 |
| Machinery oil | 4 |
| AEO-3(nonionogenic tenside) | 0.3 |
| AEO-7(nonionogenic tenside) | 0.2 |
| AEO-9(nonionogenic tenside) | 0.5 |
| Monoethanolamine borate | 8 |
| Sodium carbonate | 2 |
| Polyoxyethylene glycol | 0.8 |
| Sodium cellulose glycolate | 0.8 |
| Propyl carbinol | 0.8 |
| Deionized water | 74.6 |
Embodiment 4:
(1) in four-hole boiling flask, add 7.5g silicone oil, then add successively 0.15g AES, 0.60g AEO-3, heated and stirred, rotating speed is controlled at 300r/min, and temperature is controlled at 70 ℃.
(2) 15g monoethanolamine borate, 10g trolamine, 2g polyoxyethylene glycol are dissolved in appropriate deionized water successively, treat to dissolve completely, be slowly added drop-wise in (1).
(3) mixed solution in (2) is continued to constant temperature and stir 1h.
(4) stir the backward above-mentioned solution of end and add 2g sodium cellulose glycolate, 3g n-hexyl alcohol, 10g ammoniacal liquor, supplies surplus deionized water to 250g, continues permanent rotating speed stirring at normal temperature 30min..
The formula composition of table four embodiment 4
| Component title | Content, %(m/m) |
| Trolamine | 4 |
| Silicone oil | 3 |
| AEO-3(nonionogenic tenside) | 0.24 |
| AES(anion surfactant) | 0.06 |
| Monoethanolamine borate | 6 |
| Ammoniacal liquor | 4 |
| Polyoxyethylene glycol | 0.8 |
| Sodium cellulose glycolate | 0.8 |
| N-hexyl alcohol | 1.2 |
| Deionized water | 79.9 |
Embodiment 5:
(1) in four-hole boiling flask, add 7.5g vegetables oil, then add successively 1.5g tween 80 and 1g sorbester p17, heated and stirred, rotating speed is controlled at 500r/min, and temperature is controlled at 50 ℃.
(2) 15g monoethanolamine borate, 25g trolamine, 2g polyoxyethylene glycol are dissolved in appropriate deionized water successively, treat to dissolve completely, be slowly added drop-wise in (1).
(3) mixed solution in (2) is continued to constant temperature and stir 1h.
(4) stir the backward above-mentioned solution of end and add 2g sodium cellulose glycolate, 3g n-hexyl alcohol, 10g ammoniacal liquor, supplies surplus deionized water to 250g, and the rotating speed that slows down, to 200r/min, continues stirring at normal temperature 30min..
The formula composition of table five embodiment 5
| Component title | Content, %(m/m) |
| Trolamine | 10 |
| Vegetables oil | 3 |
| Tween 80 (nonionogenic tenside) | 0.6 |
| Sorbester p17 (nonionogenic tenside) | 0.4 |
| Monoethanolamine borate | 6 |
| Ammoniacal liquor | 4 |
| Polyoxyethylene glycol | 0.8 |
| Sodium cellulose glycolate | 0.8 |
| N-hexyl alcohol | 1.2 |
| Deionized water | 73.2 |
Embodiment 6(total mass 250g)
(1) in four-hole boiling flask, add 7.5g white oil, then add successively 0.75g AEO-3,0.5g AEO-7,1.25g AEO-9, heated and stirred, rotating speed is controlled at 500r/min, and temperature is controlled at 50 ℃.
(2) 5g sodium carbonate, 30g monoethanolamine borate, 25g trolamine, 2g polyoxyethylene glycol are dissolved in appropriate deionized water successively, treat to dissolve completely, be slowly added drop-wise in (1).
(3) mixed solution in (2) is continued to constant temperature and stir 1h.
(4) stir the backward above-mentioned solution of end and add 2g sodium cellulose glycolate, 3g n-hexyl alcohol, supply surplus deionized water to 250g, the rotating speed that slows down, to 200r/min, continues stirring at normal temperature 30min..
The formula composition of table six embodiment 6
| Component title | Content, %(m/m) |
| Trolamine | 10 |
| White oil | 3 |
| AEO-3(nonionogenic tenside) | 0.3 |
| AEO-7(nonionogenic tenside) | 0.2 |
| AEO-9(nonionogenic tenside) | 0.5 |
| Monoethanolamine borate | 12 |
| Sodium carbonate | 2 |
| Polyoxyethylene glycol | 0.8 |
| Sodium cellulose glycolate | 0.8 |
| N-hexyl alcohol | 1.2 |
| Deionized water | 69.2 |
Although, above in embodiment, the present invention is described in detail, can make on this basis some and revise, these modifications or improvements on the basis that does not depart from spirit of the present invention, all belong to the scope of protection of present invention.
Performance test:
The rust protection liquid of the present embodiment system is carried out to performance measurement, and make comparisons with commercially available prod D, commercially available prod D is the metal rust-inhibiting liquid take nitrite as main rust-preventive agent.Wherein property indices is measured respectively as follows:
Test method (SH0365-92):
1. rust prevention test
Present method is for checking the antirust ability of the rust protection liquid having made to metal.
Key instrument and material: radiator valve, wetting groove, corundum cloth, test piece (No. 45 specification: 50mm × 25mm × 2mm of steel disc), absorbent cotton, gasoline, washing analytical pure ethanol, beaker for washing.
Testing sequence:
(1) test piece is polished with gauze, after cleaning with gasoline → gasoline → ethanol → ethanol successively, dry up, stand-by.
(2) in beaker, prepare the rust protection liquid 100ml of 4% concentration, dip the solution having prepared with round end glass stick, in processed good test piece, drip 5, every diameter is 4～5mm, between each, should keep certain distance, must not connect.Get a test piece simultaneously and make blank.
(3) test piece is dried and put on the porcelain plate of moistening groove afterwards, build after moistening groove lid, be placed in standing placement under 35 ± 2 ℃ of conditions.
After standing 3 days, all there is not rust staining in test piece entirety, and in order to shorten the test period, we adjust above-mentioned (3) step, imitates mal-condition, sprays salt fog in test piece, is adjusted into following (4) step.
(4) the NaCl solution of preparation 1%, is sprayed on and is dripped in better test piece with atomizer.After test piece is dried, put on the porcelain plate of moistening groove, build after moistening groove lid, be placed in standing placement under 35 ± 2 ℃ of conditions.
After trial period (one month) is full, observe test piece situation.
The test of table one rustless property
| Antirust product | There is corrosion spot number | Rank | Whether qualified |
| Commercially available prod D | 1 | A | Qualified |
| The embodiment of the present invention 1 | 0 | A | Qualified |
| The embodiment of the present invention 2 | 0 | A | Qualified |
| The embodiment of the present invention 3 | 0 | A | Qualified |
| The embodiment of the present invention 4 | 0 | A | Qualified |
| The embodiment of the present invention 5 | 0 | A | Qualified |
| The embodiment of the present invention 6 | 0 | A | Qualified |
2. corrosion-resistanting test
Present method is that tinsel is soaked in rust protection liquid at a certain temperature, after the specified time, with metal testing plate colour-change, evaluates the antiseptic property of rust protection liquid to metal.
Key instrument and material: thermostat water bath, absorbent cotton, test piece (No. 45 specification: 50mm × 25mm × 2mm of steel disc).
Testing sequence:
(1) test piece is polished with gauze, after cleaning with gasoline → gasoline → ethanol → ethanol successively, dry up, stand-by.
(2) test piece is put into the rust protection liquid bottle that fills 4% concentration, make rust protection liquid exceed the about 10mm in test piece top, then build bottle cap, put in the water bath with thermostatic control of 55 ± 2 ℃ and test.
After trial period (one month) is full, observe test piece situation.
The test of table two antiseptic property
| Antirust product | Soak time/sky | Outward appearance | Whether qualified |
| Commercially available prod D | 30 | Rustless, than slightly dark before | Defective |
| The embodiment of the present invention 1 | 30 | Rustless, light newly as before | Qualified |
| The embodiment of the present invention 2 | 30 | Rustless, light newly as before | Qualified |
| The embodiment of the present invention 3 | 30 | Rustless, light newly as before | Qualified |
| The embodiment of the present invention 4 | 30 | Rustless, light newly as before | Qualified |
| The embodiment of the present invention 5 | 30 | Rustless, light newly as before | Qualified |
| The embodiment of the present invention 6 | 30 | Rustless, light newly as before | Qualified |
Claims (10)
1. a micro-emulsion type water-based metal antirust liquid, is characterized in that, mass percent is composed as follows:
2. micro-emulsion type water-based metal antirust liquid according to claim 1, is characterized in that, described base oil is one or more in machinery oil, vegetables oil, white oil, silicone oil, kerosene.
3. micro-emulsion type water-based metal antirust liquid according to claim 1, is characterized in that, described rust-preventive agent is organic corrosion inhibitor.
4. micro-emulsion type water-based metal antirust liquid according to claim 3, is characterized in that, described organic corrosion inhibitor is fatty acid soaps, sulfonate, one or more in alcamines, acid amides, ester class, borate.
5. micro-emulsion type water-based metal antirust liquid according to claim 4, is characterized in that, described organic corrosion inhibitor is fatty acid soaps, sulfonate, two or more in alcamines, acid amides, ester class, borate.
6. micro-emulsion type water-based metal antirust liquid according to claim 1, it is characterized in that, described tensio-active agent is one or more in Sodium dodecylbenzene sulfonate, polyoxyethylenated alcohol sodium sulfate, sorbitan fatty acid ester Soxylat A 25-7, sorbitan fatty acid ester, fatty alcohol-polyoxyethylene ether.
7. according to the micro-emulsion type water-based metal antirust liquid described in claim 1 or 6, it is characterized in that, described tensio-active agent is that anion surfactant and nonionogenic tenside are composite.
8. according to the micro-emulsion type water-based metal antirust liquid described in arbitrary claim in claim 1 to 5, it is characterized in that, mass percent is composed as follows:
9. according to the micro-emulsion type water-based metal antirust liquid described in arbitrary claim in claim 1 to 5, it is characterized in that, mass percent is composed as follows:
10. according to the micro-emulsion type water-based metal antirust liquid described in arbitrary claim in claim 1 to 5, it is characterized in that, mass percent is composed as follows:
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